F.-L. Qing et al. / Journal of Fluorine Chemistry 113 22002) 139±141
141
was stirred at 60 8C for 4 h. Then the solution was distilled to
give 4 as a colorless liquid 038.3 g, 80% yield, bp 105±
110 8C/40 mmHg).
benzoic acid were extracted with 1 M NaOH. The chloro-
form solution was washed with water and dried over
anhydrous Na2SO4. The solvent was removed in vacuo.
Puri®cation of the residue by column chromatography on
silica gel and elution with 8:1 hexane:ethyl acetate gave
3.3. 1H,1H,2H,2H-perfluorooctyltriallylsilane 22)
1
compounds 1b 00.32 g, 62% yield). H NMR0300 MHz,
Under a nitrogen atmosphere and at 0±5 8C, the solution
of allyl bromide 030 ml) in dry ether 030 ml) was added
dropwise to a mixture of magnesium 010.0 g) and dry ether
0150 ml). After the addition, the reaction mixture was stirred
at 0±5 8C for 2 h. Under a nitrogen atmosphere, the allyl-
magnesium bromide solution was transferred to a dropping
funnel and then was slowly added to a mixture of 4 024.5 g,
0.05 mol) and dry ether 0150 ml) at re¯ux. The reaction
mixture was stirred at re¯ux for 24 h. The saturated aqueous
ammonium chloride was slowly added to the reaction mix-
ture. The organic layer was separated and the water layer
was extracted with ether. The combined organic layer was
washed with water, brine, dried over anhydrous MgSO4 and
distilled to yield 2 020.4 g, 82% yield, 88±90 8C/0.7 mmHg).
1H NMR0300 MHz, CDCl 3) d: 0.83±0.89 0m, 2H), 1.64 0d,
J 8:0 Hz, 6H), 2.06±2.12 0m, 2H), 4.90±4.96 0m, 6H),
5.71±5.85 0m, 3H) ppm. IR0thin ®lm) 2978, 1633, 1241,
1210, 1145, 901, 810 cmÀ1; MS m/z 389 02), 289 06), 151
011), 101 0100); Anal. Calcd. for C17H19F13Si: C, 40.97; H,
3.84. Found: C, 40.90; H, 3.84%.
CDCl3) d: 0.97±1.00 0m, 2H), 1.15±1.19 0m, 6H), 2.10±2.25
0m, 2H), 2.42±2.46 0m, 3H), 2.83±2.90 0m, 3H), 3.05±3.10
0m, 3H) ppm. 19F NMR0282 MHz, CDCl 3) d: À1.6 0s, 3F),
33.2 0m, 2F), 39.6 0s, 2F), 41.2 0s, 4F), 44.2 0s, 2F) ppm. IR
0thin ®lm) 2992, 2923, 1240, 1207, 1145, 1070, 932,
845 cmÀ1; MS m/z 546 0M , 2), 489 074), 161 035), 81
0100); Anal. Calcd. for C17H19F13SiO3: C, 37.37; H, 3.48.
Found: C, 37.34; H, 3.41%.
3.6. 1c
A 25 ml three-necked round-bottomed ¯ask with a mag-
neticstirrerandanitrogeninletwaschargedwithNMNOÁH2O
00.7 g, 5.2 mmol), water 01 ml) and acetone 06 ml). To this
solution was added osmium tetraoxide 00.06 ml) and 2 00.5 g,
1 mmol).The reaction mixture was stirred at room tempera-
ture overnight. The saturated aqueous ammonium chloride
was slowly added to the reaction mixture. The mixture was
extracted with dichloromethane. The organic layer was
washed with aqueous Na2S2O4 and dried over anhydrous
Na2SO4. The solvent was removed in vacuo. Puri®cation of
the residue by column chromatography on silica gel and
elution with 4:1 dichloromethane:methanol gave compounds
3.4. 1a
1
Under a nitrogen atmosphere and at 10 8C, a solution of 2
07.5 g, 15 mmol) in anhydrous THF 090 ml) was slowly
added dropwise to a solution of BH3. THF 027 ml, 1 M in
THF) in THF 045 ml). After the mixture was stirred at room
temperature for 3 h, 3 M NaOH 030 ml) and then 30% H2O2
04.5 ml) were added to the mixture at 20 8C. After stirring
for 2 h, water 0100 ml) was added to the mixture. The
mixture was extracted with dichloromethane. The combined
organic layer was washed with water and dried over anhy-
drous MgSO4. The solvent was removed in vacuo. Puri®ca-
tion of the residue by column chromatography on silica gel
and elution with 15:1 dichloromethane:methanol gave com-
pounds 1a 06.3 g, 76% yield). 1H NMR0300 MHz, CDCl 3)
d: 0.55±0.62 0m, 6H), 0.72±0.80 0m, 2H), 1.52±1.61 0m, 6H),
1.98±2.05 0m, 5H), 3.62 0t, J 7:0 Hz, 6H) ppm. 19F NMR
0282 MHz, CDCl3) d: 3.9 0s, 3F), 38.2 0m, 2F), 45.1 0s, 2F),
46.2 0s, 4F), 49.2 0s, 2F) ppm. IR0thin ®lm) 3338, 2930, 2875,
1239, 1210, 1145,1065, 894, 745 cmÀ1;MSm/z493098), 477
098), 289 042); 239 093), 107 0100); Anal. Calcd. for
C17H25F13SiO3: C, 36.96;H, 4.53. Found:C, 37.13;H, 4.57%.
1c 00.4 g, 67% yield). H NMR0300 MHz, CD 3SOCD3) d:
0.67±0.70 0m, 2H), 0.87±0.90 0m, 6H), 2.35±2.45 0m, 2H),
3.20±3.30 0m, 6H), 3.60 0br, 3H), 4.45±4.52 0m, 6H) ppm. 19
F
NMR0282 MHz, CD 3SOCD3) d: À1.6 0s, 3F), 33.2 0m, 2F),
39.6 0s, 2F), 41.2 0s, 4F), 44.2 0s, 2F) ppm. IR0thin ®lm) 3385,
2978,1261,1211,1145,1022,869,803 cmÀ1;MSm/z53101),
43102),121028),410100);Anal.Calcd.forC17H25F13SiO6:C,
34.00; H, 4.19. Found: C, 34.27; H, 4.08%.
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To a solution of 3-chloroperbenzoic acid 00.86 g,
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